Desulfurization and sorbents for same

ABSTRACT

Attrition resistant, sorbent compositions for the removal of elemental sulfur and sulfur compounds, such as hydrogen sulfide and organic sulfides, from cracked-gasoline and diesel fuels are prepared by the impregnation of a sorbent support comprising zinc oxide, expanded perlite, and alumina with a promoter such as nickel, nickel oxide or a precursor of nickel oxide followed by reduction of the valence of the promoter metal in the resulting promoter metal sorbent support composition.

FIELD OF THE INVENTION

[0001] This application is a continuation-in-part of application Ser.No. 10/072,209, filed Feb. 6, 2002 still pending, which is acontinuation-in-part of application Ser. No. 09/580,611, filed May 30,2000, pending.

[0002] This invention relates to the removal of sulfur from fluidstreams of cracked-gasolines and diesel fuels. In another aspect, thisinvention relates to sorbent compositions suitable for use in thedesulfurization of fluid streams of cracked-gasolines and diesel fuels.A further aspect of this invention relates to a process for theproduction of sulfur sorbents for use in the removal of sulfur bodiesfrom fluid streams of cracked-gasolines and diesel fuels.

BACKGROUND OF THE INVENTION

[0003] The need for cleaner burning fuels has resulted in a continuingworld-wide effort to reduce sulfur levels in hydrocarbon-containingfluids such as gasoline and diesel fuels. The reduction of sulfur insuch hydrocarbon-containing fluids is considered to be a means forimproving air quality because of the negative impact the sulfur has onthe performance of sulfur-sensitive items such as automotive catalyticconverters. The presence of oxides of sulfur in automotive engineexhaust inhibits and may irreversibly poison noble metal catalysts inthe converter. Emissions from an inefficient or poisoned convertercontain levels of non-combusted, non-methane hydrocarbons, oxides ofnitrogen, and carbon monoxide. Such emissions are catalyzed by sunlightto form ground level ozone, more commonly referred to as smog.

[0004] Most of the sulfur in a hydrocarbon-containing fluid such asgasoline comes from thermally processed gasolines. Thermally processedgasolines such as, for example, thermally cracked gasoline, visbreakergasoline, coker gasoline and catalytically cracked gasoline (hereinaftercollectively referred to as “cracked-gasoline”) contains, in part,olefins, aromatics, sulfur, and sulfur-containing compounds.

[0005] Since most gasolines, such as for example automobile gasolines,racing gasolines, aviation gasolines, boat gasolines, and the likecontain a blend of, at least in part, cracked-gasoline, reduction ofsulfur in cracked-gasoline will inherently serve to reduce the sulfurlevels in most gasolines such as, for example, automobile gasolines,racing gasolines, aviation gasolines, boat gasolines, and the like.

[0006] The public discussion about gasoline sulfur has not centered onwhether or not sulfur levels should be reduced. A consensus has emergedthat lower sulfur gasoline reduces automotive emissions and improves airquality. Thus, the real debate has focused on the required level ofreduction, the geographical areas in need of lower sulfur gasoline, andthe time frame for implementation.

[0007] As the concern over the impact of automotive air pollutioncontinues, it is clear that further efforts to reduce the sulfur levelsin automotive fuels will be required. While the current gasolineproducts contain about 330 parts per million (ppm), the U. S.Environmental Protection Agency recently issued regulations requiringthe average sulfur content in gasoline to be less than 30 ppm averagewith an 80 ppm cap. By 2006, the standards will effectively requireevery blend of gasoline sold in the United States to meet the 30 ppmlevel.

[0008] In addition to the need to be able to produce low sulfur contentautomotive fuels, there is also a need for a process which will have aminimal effect on the olefin content of such fuels so as to maintain theoctane number (both research and motor octane number). Such a processwould be desirable since saturation of olefins greatly affects theoctane number. Such adverse effect on olefin content is generally due tothe severe condition normally employed, such as duringhydrodesulfurization, to remove thiophenic compounds (such as, forexample, thiophenes, benzothiophenes, alkyl thiophenes,alkylbenzothiophenes, alkyl dibenzothiophenes and the like) which aresome of the most difficult sulfur-containing compounds to be removedfrom cracked-gasoline. In addition, there is a need to avoid a systemwherein the conditions are such that the aromatic content of thecracked-gasoline is also lost through saturation. Thus, there is a needfor a process wherein desulfurization is achieved and the octane numberis maintained.

[0009] In addition to the need for removal of sulfur fromcracked-gasolines, there is also presented to the petroleum industry aneed to reduce the sulfur content in diesel fuels. In removing sulfurfrom diesel fuels by hydrodesulfurization, the cetane is improved butthere is a large cost in hydrogen consumption. Such hydrogen is consumedby both hydrodesulfurization and aromatic hydrogenation reactions.

[0010] Thus, there is a need for a process of desulfurization without asignificant consumption of hydrogen so as to provide a more economicalprocess for the treatment of cracked gasolines and diesel fuels.

[0011] As a result of the lack of success in providing a successful andeconomically feasible process for the reduction of sulfur levels incracked-gasolines and diesel fuels, it is apparent that there is still aneed for a better process for the desulfurization of suchhydrocarbon-containing fluids which has minimal effect on octane levelswhile achieving high levels of sulfur removal.

[0012] Traditionally, sorbent compositions used in processes for theremoval of sulfur from hydrocarbon-containing fluids have beenagglomerates utilized in fixed bed applications. Because of the variousprocess advantages of fluidized beds, hydrocarbon-containing fluids aresometimes used in fluidized bed reactors. Fluidized bed reactors haveadvantages over fixed bed reactors such as better heat transfer andbetter pressure drop. Fluidized bed reactors generally use reactantsthat are particulates. The size of these particulates is generally inthe range of about 1 micron to about 1000 microns. However, thereactants used generally do not have sufficient attrition resistance forall applications. Consequently, finding a sorbent with sufficientattrition resistance that removes sulfur from thesehydrocarbon-containing fluids and that can be used in fluidized,transport, moving, or fixed bed reactors is desirable and would be ofsignificant contribution to the art and to the economy.

[0013] It is thus an object of the present invention to provide a novelsorbent composition that can be used for the removal of sulfur fromcracked-gasolines and diesel fuels.

[0014] Another object of the present invention is to provide a processfor the production of novel sorbent compositions which are useful in thedesulfurization of cracked-gasolines and diesel fuels.

[0015] Another object of the present invention is to provide a processfor the removal of sulfur from cracked-gasolines and diesel fuels whichminimizes the consumption of hydrogen and minimizes the saturation ofolefins and aromatics contained in such streams.

[0016] A still further object of the present invention is to provide adesulfurized cracked-gasoline that contains less than about 100 partsper million, preferably less than 50 parts per million, of sulfur basedon the weight of the desulfurized cracked-gasoline, and which containsessentially the same amount of olefins and aromatics as are in thecracked-gasoline from which such desulfurized cracked-gasoline was made.

[0017] Other aspects, objectives, and advantages of the presentinvention will be apparent from the detailed description of theinvention and the appended claims.

SUMMARY OF THE INVENTION

[0018] The present invention is based upon my discovery that through theutilization of expanded perlite to form a sorbent base compositioncomprising zinc oxide, expanded perlite and alumina, there is provided anovel base composition for the formation of a sorbent system by theaddition of a promoter metal thereto which permits both the control ofthe attrition value of the resulting sorbent system and the control ofthe sorbent system activity.

[0019] More specifically, in accordance with the present invention, Ihave discovered that use of expanded perlite as the silica source in asystem comprising zinc oxide, silica, alumina, and a promoter metalresulted in a sorbent composition which permitted variance of the zincoxide content and the alumina content of the based support compositionthereby permitted the variance of the sorbent life when used in thedesulfurization of cracked-gasolines or diesel fuels as well asachieving a variance on the attrition value of the sorbent systemthrough the altering of the alumina content of the base support.

[0020] Thus, in one aspect of the present invention, there is provided anovel sorbent composition suitable for the desulfurization ofcracked-gasolines and diesel fuels which comprises a base supportcomponent consisting essentially of zinc oxide, expanded perlite,alumina, and a promoter component wherein the valence of such promotercomponent is substantially reduced and such reduced-valence promotercomponent is present in an amount which is effective in the removal ofsulfur from cracked-gasolines or diesel fuels.

[0021] In accordance with another aspect of the present invention, thereis provided a process for the preparation of a novel sorbent systemwhich comprises contacting a base support consisting essentially of zincoxide, expanded perlite, and alumina so as to form a mixture thereofselected from the group consisting of a wet mix, a dough, a paste, or aslurry; particulating such mixture so as to form a particulate selectedfrom the group consisting of a granule, an extrudate, a tablet, asphere, a pellet, or a microsphere; drying such particulate to form adried particulate; calcining such dried particulate to form a calcinedparticulate; distributing a promoter component upon such dried andcalcined particulate to form a promoted particulate; drying suchpromoted particulate to form a dried promoted particulate; calciningsuch dried promoted particulate to form a calcined promoted particulate;and reducing such calcined promoted particulate with a suitable reducingagent, such as hydrogen, so as to produce a sorbent composition having asubstantially reduced, preferably zero-valence promoter componentdistributed on such based sorbent composition in an amount which iseffective in removing sulfur from a cracked-gasoline or diesel fuelstream. The attrition resistance of the sorbent composition can beenhanced by varying the concentration of the alumina component in thebase support. The life of the sorbent system for the desulfurization ofcracked-gasolines or diesel fuels is controlled through the control ofthe zinc oxide content of the base support component of the sorbentsystem.

[0022] In accordance with still another aspect of the present invention,there is provided an oxidized (i.e., unreduced) sorbent compositionwhich can be made by the sorbent preparation process summarized above,absent the steps after calcination of the promoted particulate. Theoxidized sorbent composition can comprise all or part of the followingcomponents: zinc oxide; expanded perlite; a substitutional solid metaloxide solution characterized by the formula M_(X)Zn_(Y)O wherein M is apromoter metal and X and Y are each numerical values in the range offrom 0.01 to 0.99; and a promoter metal-zinc aluminate substitutionalsolid solution characterized by the formula M_(Z)Zn_((1−Z))Al₂O₄ whereinM is the promoter metal and Z is a numerical value in the range of from0.01 to 0.99.

[0023] In accordance with yet another aspect of the present invention,there is provided a reduced sorbent composition which can be made by thesorbent preparation process summarized above. The reduced sorbentcomposition can comprise all or part of the following components: zincoxide; expanded perlite; a substitutional solid metal solutioncharacterized by the formula M_(A)Zn_(B) wherein M is a promoter metaland A and B are each numerical values in the range of from 0.01 to 0.99;and a promoter metal-zinc aluminate substitutional solid solutioncharacterized by the formula M_(Z)Zn_((1−Z))Al₂O₄ wherein M is thepromoter metal and Z is a numerical value in the range of from 0.01 to0.99.

[0024] In accordance with a further aspect of the present invention,there is provided a process for the desulfurization of cracked-gasolinesand diesel fuels, which comprises desulfurizing in a desulfurizationzone such a hydrocarbon-containing fluid with a sorbent composition,separating the desulfurized hydrocarbon-containing fluid from thesulfurized sorbent composition, regenerating at least a portion of thesulfurized sorbent composition to produce a regenerated, desulfurizedsorbent composition; activating at least a portion of the regenerated,desulfurized sorbent composition to produce an activated, regenerated,desulfurized sorbent composition; and thereafter returning at least aportion of the activated, regenerated, desulfurized sorbent compositionto the desulfurization zone.

DETAILED DESCRIPTION OF THE INVENTION

[0025] The present invention is based upon the discovery by applicantthat through the use of milled expanded perlite in the formation of asorbent support comprising zinc oxide, milled expanded perlite, and abinder there was produced a base support in which the zinc oxide contentand binder content could be adjusted so as to provide an attritionresistance sorbent as well as the extension of the useful life of thesorbent system.

[0026] More specifically, it was discovered that through the use ofmilled expanded perlite in the formation of a zinc oxide, crushedexpanded perlite, and a binder such as alumina there was achieved a basesupport composition which permitted the variation of the zinc oxide andbinder content therein such that following impregnation of the basesupport with a promoter metal the resulting system exhibited attritionresistance as well as extended life when following the reduction of samewith hydrogen. The resulting sorbent composition was employed in thedesulfurization of a cracked-gasoline and/or diesel fuel.

[0027] The term “gasoline” denotes a mixture of hydrocarbons boiling inthe range of from about 100° F. to about 400° F., or any fractionthereof. Examples of suitable gasoline include, but are not limited to,hydrocarbon streams in refineries such as naphtha, straight-run naphtha,coker naphtha, catalytic gasoline, visbreaker naphtha, alkylate,isomerate, reformate, and the like and combinations thereof.

[0028] The term “cracked-gasoline” denotes a mixture of hydrocarbonsboiling in the range of from about 100° F. to about 400° F., or anyfraction thereof, that are products from either thermal or catalyticprocesses that crack larger hydrocarbon molecules into smallermolecules. Examples of suitable thermal processes include, but are notlimited to, coking, thermal cracking, visbreaking, and the like andcombinations thereof. Examples of suitable catalytic cracking processesinclude, but are not limited to, fluid catalytic cracking, heavy oilcracking, and the like and combinations thereof. Thus, examples ofsuitable cracked-gasoline include, but are not limited to, cokergasoline, thermally cracked gasoline, visbreaker gasoline, fluidcatalytically cracked gasoline, heavy oil cracked gasoline, and the likeand combinations thereof. In some instances, the cracked-gasoline may befractionated and/or hydrotreated prior to desulfurization when used as ahydrocarbon-containing fluid in a process of the present invention.

[0029] The term “diesel fuel” denotes a mixture of hydrocarbons boilingin the range of from about 300° F. to about 750° F., or any fractionthereof. Examples of suitable diesel fuels include, but are not limitedto, light cycle oil, kerosene, jet fuel, straight-run diesel,hydrotreated diesel, and the like and combinations thereof.

[0030] The term “sulfur” denotes sulfur in any form such as elementalsulfur or a sulfur compound normally present in a hydrocarbon-containingfluid such as cracked gasoline or diesel fuel. Examples of sulfur whichcan be present during a process of the present invention usuallycontained in a hydrocarbon-containing fluid, include, but are notlimited to, hydrogen sulfide, carbonyl sulfide (COS), carbon disulfide(CS₂), mercaptans (RSH), organic sulfides (R-S-R), organic disulfides(R-S-S-R), thiophene, substituted thiophenes, organic trisulfides,organic tetrasulfides, benzothiophene, alkyl thiophenes, alkylbenzothiophenes, alkydibenzothiophenes, and the like and combinationsthereof as well as the heavier molecular weights of same which arenormally present in a diesel fuel of the types contemplated for use in aprocess of the present invention, wherein each R can be an alkyl orcycloalkyl or aryl group containing one carbon atom to ten carbon atoms.

[0031] The term “fluid” denotes gas, liquid, vapor, and combinationsthereof.

[0032] The term “gaseous” denotes that state in which thehydrocarbon-containing fluid, such as cracked-gasoline or diesel fuel,is primarily in a gas or vapor phase.

[0033] The term “attrition resistance” denotes the attrition resistanceof a sorbent composition of the present invention measured as theDavison Index. The term “Davison Index” (“DI”) refers to a measure of asorbent's resistance to particle size reduction under controlledconditions of turbulent motion. The Davison Index represents the weightpercent of the over 20 micrometer particle size fraction which isreduced to particle sizes of less than 20 micrometers under testconditions. The Davison Index is measured using a Jet cup attritiondetermination method. The Jet cup attrition determination methodinvolves screening a 5 gram sample of sorbent to remove particles in the0 to 20 micrometer size range. The particles above 20 micrometers arethen subjected to a tangential jet of air at a rate of 21 liters perminute introduced through a 0.0625 inch orifice fixed at the bottom of aspecially designed Jet cup (1″ I.D.×2″ height) for a period of 1 hour.The Davison Index (“DI”) is calculated as follows: $\begin{matrix}{DI} \\{factor}\end{matrix} = {\frac{\begin{matrix}\text{Weight~~of~~0~~to~~20~~micrometer} \\\text{material formed during test}\end{matrix}}{\begin{matrix}\text{Weight~~of~~original~~20+~~micrometer} \\\text{fraction being tested}\end{matrix}} \times 100 \times \text{correction}}$

[0034] Correction factor (presently 0.3) is determined by using a knowncalibration standard to adjust for differences in jet cup dimensions andwear.

[0035] The term “support component” denotes any component or combinationof such components which can be used as a support for a sorbentcomposition of the present invention to help promote the desulfurizationprocess disclosed herein. Examples of a suitable support componentinclude, but are not limited to, zinc oxide in association with asuitable binder such as alumina and expanded perlite. A presentlypreferred support component is that comprising zinc oxide, expandedperlite, and alumina.

[0036] The term “promoter component” denotes any component which can beadded to the sorbent composition of the present invention to helppromote the desulfurization of cracked-gasolines or diesel fuels. Suchpromoter components are at least one metal, metal oxide, or precursorfor the metal oxide wherein the metal component is selected from thegroup consisting essentially of nickel, cobalt, iron, manganese, copper,zinc, molybdenum, tungsten, silver, tin, antimony, and vanadium.

[0037] Some examples of promoter metal-containing compounds includemetal acetates, metal carbonates, metal nitrates, metal sulfates, metalthiocyanates, and the like and combinations thereof. Preferably, themetal of such promoter component is nickel. In a preferred embodiment ofthe present invention, the sorbent composition is promoted with aprecursor of a nickel oxide such as nickel nitrate, more preferablynickel nitrate hexahydrate.

[0038] The term “metal” denotes metal in any form such as elementalmetal or a metal-containing compound.

[0039] The term “metal oxide” denotes metal oxide in any form such as ametal oxide or a metal oxide precursor.

[0040] During the preparation of a sorbent composition of the presentinvention, the promoter component selected from the group consisting ofmetals, metal oxides, and the like and combinations thereof mayinitially be in the form of a metal-containing compound and/or a metaloxide precursor. It should be understood that when the promotercomponent is initially a metal-containing compound and/or a metal oxideprecursor, a portion of, or all of, such compound and/or precursor maybe converted to the corresponding metal or metal oxide of such compoundand/or precursor during the inventive process disclosed herein.

[0041] The term “perlite” as used herein is the petrographic term for asiliceous volcanic rock which naturally occurs in certain regionsthroughout the world. The distinguishing feature, which sets it apartfrom other volcanic minerals, is its ability to expand four to twentytimes its original volume when heated to certain temperatures. Whenheated above 1600° F., crushed perlite expands due to the presence ofcombined water with the crude perlite rock. The combined water vaporizesduring the heating process and creates countless tiny bubbles in theheat softened glassy particles. It is these diminutive glass sealedbubbles which account for its light weight. Expanded perlite can bemanufactured to weigh as little as 2.5 lbs per cubic foot.

[0042] Typical chemical analysis 1 properties of expanded perlite are:silicon dioxide 73%, aluminum oxide 17%, potassium oxide 5%, sodiumoxide 3%, calcium oxide 1%, plus trace elements.

[0043] Typical physical properties of expanded perlite are: softeningpoint 1600-2000° F., fusion point 2300° F.-2450° F., pH 6.6-6.8, andspecific gravity 2.2-2.4.

[0044] The term “expanded perlite” as used herein refers to thespherical form of perlite which has been expanded by heating the perlitesiliceous volcanic rock to a temperature above 1600° F.

[0045] The term “particulate expanded perlite” or “milled perlite” asused herein denotes that form of expanded perlite which has beensubjected to crushing so as to form a particulate mass wherein theparticle size of such mass is comprised of at least 97% of particleshaving a size of less than 2 microns.

[0046] The term “milled expanded perlite” is intended to mean theproduct resulting from subjecting expanded perlite particles to millingor crushing.

[0047] The zinc oxide will generally be present in the sorbent supportcomposition in an amount in the range of from about 10 to about 90weight percent zinc oxide based on the total weight of the sorbentcomposition, preferably in an amount in the range of from about 40 toabout 80 weight percent zinc oxide.

[0048] The zinc oxide used in the preparation of a sorbent supportcomposition of the present invention can either be in the form of zincoxide or in the form of one or more zinc compounds that are convertibleto zinc oxide under the conditions of preparation described herein.Examples of suitable zinc compounds include, but are not limited to,zinc sulfide, zinc sulfate, zinc hydroxide, zinc carbonate, zincacetate, zinc nitrate, and the like and combinations thereof.Preferably, the zinc oxide is in the form of powdered zinc oxide.

[0049] The alumina used in preparing a sorbent support composition ofthe present invention can be any suitable commercially available aluminamaterial including, but not limited to, colloidal alumina solutions andgenerally those alumina compounds produced by the dehydration of aluminahydrates.

[0050] In preparing the sorbent support component of the subjectinvention, there is generally employed an amount of alumina in the rangeof about 1.0 to about 20 weight percent, preferably an amount in therange of about 5 to about 15 weight percent, based on the total weightof the sorbent support component.

[0051] The expanded perlite will generally be present in the sorbentsupport composition in an amount in the range of from about 10 to about40 weight percent perlite based on the weight of the sorbent supportcomposition, preferably in an amount in the range of from about 15 toabout 30 weight percent.

[0052] The promoter component will generally be present in the sorbentcomposition in an amount in the range of from about 1.0 to about 60weight percent promoter component based on the total weight of thesorbent composition, preferably in an amount in the range of from about10 to about 30 weight percent promoter component. When the promotercomponent comprises a bimetallic promoter component, the bimetallicpromoter component should comprise a ratio of the two metals formingsuch bimetallic promoter component in the range of from about 20:1 toabout 1:20. In a presently preferred embodiment of the presentinvention, the promoter component is a bimetallic promoter componentcomprising nickel and cobalt in a weight ratio of about 1:1.

[0053] In the manufacture of a sorbent composition of the presentinvention, the support component is generally prepared by combining thecomponents of the support component, zinc oxide, expanded perlite, andalumina in appropriate proportions by any suitable method or mannerwhich provides for the intimate mixing of such components to therebyprovide a substantially homogeneous mixture comprising zinc oxide,expanded perlite, and alumina. Any suitable means for mixing thecomponents of the support component can be used to achieve the desireddispersion of such components. Examples of suitable mixing meansinclude, but are not limited to, mixing tumblers, stationary shells ortroughs, Muller mixers, which are of the batch or continuous type,impact mixers, and the like. It is presently preferred to use a Mullermixer in the mixing of the components of the support component.

[0054] The components of the support component are mixed to provide aresulting mixture which can be in a form selected from the groupconsisting of wet mix, dough, paste, slurry, and the like. Suchresulting mixture can then be shaped to form a particulate selected fromthe group consisting of a granule, an extrudate, a tablet, a sphere, apellet, or a microsphere. For example, if the resulting mixture is inthe form of a wet mix, the wet mix can be densified, dried under adrying condition as disclosed herein, calcined under a calciningcondition as disclosed herein, and thereafter shaped, or particulated,through the granulation of the densified, dried, calcined mix to formgranulates. Also for example, when the mixture of the components of thesupport component results in a form of a mixture which is either in adough state or paste state, such mixture can then be shaped, preferablyextruded, to form a particulate, preferably cylindrical extrudateshaving a diameter in the range of from about {fraction (1/32)} inch to ½inch and any suitable length, preferably a length in the range of fromabout ⅛ inch to about 1 inch. The resulting particulates, preferablycylindrical extrudates, are then dried under a drying condition asdisclosed herein and then calcined under a calcining condition asdisclosed herein. More preferably, when the mix is in the form of aslurry, the particulation of such slurry is achieved by spray drying theslurry to form microspheres thereof having a size in the range of fromabout 20 to about 500 microns. Such microspheres are then subjected todrying under a drying condition as disclosed herein and calcining undera calcining condition as disclosed herein.

[0055] When the particulation is achieved by preferably spray drying, adispersant component may be utilized and can be any suitable compoundthat helps to promote the spray drying ability of the mix which ispreferably in the form of a slurry. In particular, these components areuseful in preventing deposition, precipitation, settling, agglomerating,adhering, and caking of solid particles in a fluid medium. Suitabledispersants include condensed phosphates, sulfonated polymers, andcombinations thereof. The term condensed phosphates refers to anydehydrated phosphate where the H₂O:P₂O₅ is less than about 3:1. Specificexamples of suitable dispersants include sodium pyrophosphate, sodiummetaphosphate, sulfonated styrene maleic anhydride polymer, andcombinations thereof. The amount of a dispersant component used isgenerally in the range of from about 0.01 weight percent based on thetotal weight of the components to about 10 weight percent. Preferably,the amount of a dispersant component used is generally in the range offrom about 0.1 weight percent to about 8 weight percent.

[0056] The alumina component of the base support can be any suitablecompound of alumina that has cement-like properties which can help tobind the particulate composition together. Presently preferred isalumina, preferably peptized alumina.

[0057] In the practice of the present invention, it is presentlypreferred that the sorbent composition be formed through spray drying.In preparing the preferred spray-dried sorbent composition, an acidcomponent can be used. In general, the acid component can be an organicacid or a mineral such as nitric acid. If the acid component is anorganic acid, it is preferred to be a carboxylic acid. If the acidcomponent is a mineral acid, it is preferred to be a nitric acid or aphosphoric acid. Mixtures of these acids can also be used. Generally,the acid is used with water to form a dilute aqueous acid solution. Theamount of acid in the acid component is generally in the range of fromabout 0.01 volume percent based on the total volume of the acidcomponent to about 20 volume percent.

[0058] In preparing the preferred spray-dried sorbent composition a basesupport component, comprising zinc oxide, expanded perlite, and aluminacan be contacted together in any manner known in the art that will forma mixture that is a liquid solution, a slurry, or a paste that iscapable of being dispersed in a fluid-like spray. When a base supportcomponent is a solid, then it should be contacted in a liquid medium toform a mixture that is a liquid solution, a slurry, or a paste that iscapable of being dispersed in a fluid-like spray. Suitable means forcontacting these components are known in the art such as, for example,tumblers, stationary shells, troughs, Muller mixers, impact mixers, andthe like.

[0059] Generally, these components, after contacting to form a mixture,are contacted with an acid component as described hereinabove. However,the dry components and the acid component can be contacted togethersimultaneously or separately.

[0060] After the components are contacted together to form a mixture,they are subjected to spray drying to form a spray-dried sorbentmaterial having particles, preferably in the form of micro-spheres, thathave a mean particle size in the ranges as disclosed herein. Spraydrying is known in the art and is discussed in Perry's ChemicalEngineers' Handbook, Sixth Edition, published by McGraw-Hill, Inc., atpages 20-54 through 20-58, which pages are incorporated herein byreference. Additional information can be obtained from the Handbook ofIndustrial Drying, published by Marcel Dekker Inc., at pages 243 through293.

[0061] The spray-dried sorbent material can then be dried under a dryingcondition as disclosed herein and then calcined, preferably in anoxidizing atmosphere such as in the presence of oxygen or air, under acalcining condition as disclosed herein to form a calcined, spray-driedsorbent material. The calcination can be conducted under any suitablecondition that removes residual water and oxidizes any combustibles.Usually, the spray-dried base sorbent material is calcined in anoxygen-containing atmosphere.

[0062] When the particulate support component comprising zinc oxide,perlite, and alumina is calcined, at least a portion of the zinc oxideand at least a portion of the alumina combine to form zinc aluminate(ZnAl₂O₄). The resulting calcined support component preferably compriseszinc aluminate in an amount in the range of from about 2 to about 50weight percent, more preferably in the range of from about 5 to about 30weight percent, and most preferably in the range of from 10 to 20 weightpercent. The calcined support component preferably comprises zinc oxidein an amount in the range of from about 20 to about 95 weight percent,more preferably in the range of from about 40 to about 90 weightpercent, and most preferably in the range of from about 60 to about 80weight percent. The calcined support component, preferably comprisesperlite in an amount in the range of from about 2 to about 50 weightpercent, more preferably in the range of from about 5 to about 30 weightpercent, and most preferably in the range of from 10 to 20 weightpercent.

[0063] Generally, the spray-dried sorbent material has a mean particlesize in the range of from about 10 micrometers to about 1000micrometers, preferably in the range of from about 20 micrometers toabout 150 micrometers.

[0064] The term “mean particle size” refers to the size of theparticulate material as determined by using a RO-TAP® Testing SieveShaker, manufactured by W. S. Tyler Inc., of Mentor, Ohio, or othercomparable sieves. The material to be measured is placed in the top of anest of standard eight inch diameter stainless steel frame sieves with apan on the bottom. The material undergoes sifting for a period of about10 minutes; thereafter, the material retained on each sieve is weighed.The percent retained on each sieve is calculated by dividing the weightof the material retained on a particular sieve by the weight of theoriginal sample. This information is used to compute the mean particlesize.

[0065] The resulting particulate (preferably spray-dried) calcinedsupport component comprising zinc aluminate, zinc oxide, crushedexpanded perlite, and optionally a binder, preferably alumina (if notall converted to zinc aluminate), is then incorporated with a promotercomponent.

[0066] The promoter component which is useful in the practice of thepresent invention is promoter derived from one or more metals, metaloxides, or metal oxide precursors wherein the metal is selected from thegroup consisting of cobalt, nickel, iron, manganese, zinc, copper,molybdenum, silver, tin, vanadium, and antimony. Presently preferred isa promoter component of nickel or cobalt or a mixture of cobalt andnickel.

[0067] Following the incorporating of the particulated, calcined supportcomponent, preferably by impregnation, with a promoter component, theresulting promoted particulates are then subjected to drying under adrying condition as disclosed herein and calcined under a calciningcondition as disclosed herein prior to the subjecting of such dried,calcined, promoted particulates to reduction with a reducing agent,preferably hydrogen.

[0068] The promoter component(s) may be incorporated onto, or with, theparticulated (preferably spray-dried), calcined support component by anysuitable means or method(s) for incorporating the promoter component(s)onto, or with, a substrate material, such as the dried and calcinedparticulates, which results in the formation of a promoted sorbentcomposition which can then be dried under a drying condition asdisclosed herein and calcined under a calcining condition as disclosedherein to thereby provide dried, calcined, promoted particulates. Thedried, calcined, promoted particulates can then be subjected toreduction with a reducing agent, preferably hydrogen, to thereby providea sorbent composition of the present invention. Examples of means forincorporating the promoter component include impregnating, soaking orspraying, and combinations thereof.

[0069] A preferred method of incorporating is impregnating using anystandard incipient wetness impregnation technique (i.e., essentiallycompletely filling the pores of a substrate material with a solution ofthe incorporating elements) for impregnating a substrate. A preferredmethod uses an impregnating solution comprising the desirableconcentration of a promoter component so as to ultimately provide apromoted particulate which can then be subjected to drying and calciningfollowed by reduction with a reducing agent such as hydrogen. Theimpregnating solution can be any aqueous solution and amounts of suchsolution which suitably provides for the impregnation of theparticulates of support component to give an amount of promotercomponent that provides, after reduction with a reducing agent, areduced promoter component content sufficient to permit the removal ofsulfur from cracked-gasoline or diesel fuel when such fluid is treatedin accordance with a desulfurization process of the present invention.

[0070] It can be desirable to use an aqueous solution of a promotercomponent for the impregnation of the particulates. A preferredimpregnating solution comprises an aqueous solution formed by dissolvinga metal-containing compound, preferably such metal-containing compoundis in the form of a metal salt, such as, a metal chloride, a metalnitrate, a metal sulfate, and the like and combinations thereof, in asolvent, such as, water, alcohols, esters, ethers, ketones, andcombinations thereof.

[0071] The concentration of the metal promoter component in the aqueoussolution can be in the range of from about 0.1 gram of metal promotercomponent per gram of aqueous solution to about 5 grams of metalpromoter component per gram of aqueous solution. Preferably, the weightratio of metal promoter component to the aqueous medium of such aqueoussolution can be in the range of from about 1:1 to about 4:1 but, morepreferably, it is in the range of from 1.5:1 to 3:1.

[0072] In preparing the spray-dried sorbent material, a promotercomponent can be added to the spray-dried sorbent material as acomponent of the original mixture, or they can be added after theoriginal mixture has been spray dried and calcined. If a promotercomponent is added to the spray-dried sorbent material after it has beenspray dried and calcined, the spray-dried sorbent material should bedried and calcined a second time. The spray-dried sorbent material ispreferably dried a second time at a temperature generally in the rangeof from about 100° F. to about 650° F. Preferably, the spray-driedsorbent material can be dried a second time at a temperature generallyin the range of from about 150° F. to about 600° F. and, morepreferably, in the range of from 200° F. to 550° F. The time period forconducting the drying a second time is generally in the range of fromabout 0.5 hour to about 8 hours, preferably in the range of from about 1hour to about 6 hours and, more preferably, in the range of from 1.5hours to 4 hours. Such drying a second time is generally carried out ata pressure in the range of from about atmospheric (i.e., about 14.7pounds per square inch absolute) to about 100 pounds per square inchabsolute (psia), preferably about atmospheric. This spray-dried sorbentmaterial is then calcined, preferably in an oxidizing atmosphere such asin the presence of oxygen or air, under a calcining condition asdisclosed herein.

[0073] A preferred impregnating solution is formed by dissolving ametal-containing compound (such as nickel nitrate hexahydrate) in water.It is acceptable to use somewhat of an acidic solution to aid in thedissolution of the metal-containing compound. It is preferred for theparticulates to be impregnated with a nickel component by use of asolution containing nickel nitrate hexahydrate dissolved in water.

[0074] Generally, a drying condition, as referred to herein, can includea temperature in the range of from about 180° F. to about 290° F.,preferably in the range of from about 190° F. to about 280° F. and, mostpreferably, in the range of from 200° F. to 270° F. Such dryingcondition can also include a time period generally in the range of fromabout 0.5 hour to about 60 hours, preferably in the range of from about1 hour to about 40 hours and, most preferably, in the range of from 1.5hours to 20 hours. Such drying condition can also include a pressuregenerally in the range of from about atmospheric (i.e., about 14.7pounds per square inch absolute) to about 150 pounds per square inchabsolute (psia), preferably in the range of from about atmospheric toabout 100 psia, most preferably about atmospheric, so long as thedesired temperature can be maintained. Any drying methods(s) known toone skilled in the art such as, for example, air drying, heat drying,and the like and combinations thereof can be used.

[0075] Generally, a calcining condition, as referred to herein, caninclude a temperature in the range of from about 700° F. to about 1600°F., preferably in the range of from about 800° F. to about 1500° F. and,more preferably, in the range of from 900° F. to about 1400° F. Suchcalcining condition can also include a pressure, generally in the rangeof from about 7 pounds per square inch absolute (psia) to about 750psia, preferably in the range of from about 7 psia to about 450 psiaand, most preferably, in the range of from 7 psia to 150 psia, and atime period in the range of from about 1 hour to about 60 hours,preferably for a time period in the range of from about 2 hours to about20 hours and, most preferably, for a time period in the range of from 3hours to 15 hours.

[0076] When the promoted particulates are calcined, at least a portionof the promoter metal and at least a portion of the zinc aluminatecombine to form a promoter metal-zinc aluminate substitutional solidsolution characterized by the formula: M_(Z)Zn_((1−Z))Al₂O₄, wherein Mis the promoter metal and Z is a numerical value in the range of from0.01 to 0.99. Further, upon calcination, at least a portion of thepromoter metal and at least a portion of the zinc oxide combine to forma substitutional solid metal oxide solution characterized by theformula: M_(X)Zn_(Y)O, wherein M is the promoter metal, X is a numericalvalue in the range of from 0.01 to 0.99, and Y is a numerical value inthe range of from 0.01 to 0.99. In the above formula, it is preferredfor X to be in the range of from about 0.50 to about 0.90, morepreferably from about 0.60 to about 0.80, and most preferably from 0.65to 0.75. It is further preferred for Y to be in the range of from about0.10 to about 0.50, more preferably from about 0.20 to about 0.40, andmost preferably from 0.25 to 0.35. Preferably, Y is equal to (1−X).

[0077] Substitutional solid solutions have unique physical and chemicalproperties that are important to the chemistry of the inventive sorbentcomposition described herein. Substitutional solid solutions are asubset of alloys that are formed by the direct substitution of thesolute metal for the solvent metal atoms in the crystal structure. Forexample, it is believed that the promoter metal-zinc oxidesubstitutional solid metal oxide solution found in the oxidized (i.e.,unreduced), calcined sorbent composition of the present invention isformed by the solute zinc metal atoms substituting for the solventpromoter metal atoms. There are three basic criteria that favor theformation of substitutional solid solutions: (1) the atomic radii of thetwo elements are within 15 percent of each other; (2) the crystalstructures of the two pure phases are the same; and (3) theelectronegativities of the two components are similar. The promotermetal (as the elemental metal or metal oxide) and zinc oxide employed inthe inventive sorbent composition preferably meet at least two of thethree criteria set forth above. For example, when the promoter metal isnickel, the first and third criteria, are met, but the second is not.The nickel and zinc metal atomic radii are within 10 percent of eachother and the electronegativities are similar. However, nickel oxide(NiO) preferentially forms a cubic crystal structure, while zinc oxide(ZnO) prefers a hexagonal crystal structure. A nickel zinc oxide solidsolution retains the cubic structure of the nickel oxide. Forcing thezinc oxide to reside in the cubic structure increases the energy of thephase, which limits the amount of zinc that can be dissolved in thenickel oxide structure. This stoichiometry control manifests itselfmicroscopically in a 70:30 nickel zinc oxide solid solution(Ni_(0.7)Zn_(3.0)O) that is formed during oxidation (i.e., calcinationor regeneration) and microscopically in the repeated regenerability ofthe sorbent.

[0078] The calcined (i.e., oxidized or regenerated), promoted sorbentparticulates preferably comprise the substitutional solid metal oxidesolution (M_(X)Zn_(Y)O) in an amount in the range of from about 5 toabout 70 weight percent, more preferably in the range of from about 10to about 60 weight percent, still more preferably in the range of fromabout 20 to about 40 weight percent, and most preferably in the range of25 to 35 weight percent. The calcined, promoted sorbent particulatespreferably comprise the promoter metal-zinc aluminate substitutionalsolid solution (M_(Z)Zn_((1−Z))Al₂O₄) in an amount in the range of fromabout 2 to about 50 weight percent, more preferably in the range of fromabout 5 to about 30 weight percent, and most preferably in the range offrom 10 to 20 weight percent. The calcined, promoted sorbentparticulates preferably comprise zinc oxide in an amount in the range offrom about 10 to about 90 weight percent, more preferably in the rangeof from about 20 to about 70 weight percent, still more preferably inthe range of from about 30 to about 50 weight percent, and mostpreferably in the range of from 35 to 45 weight percent. The calcined,promoted sorbent particulates preferably comprise perlite in an amountin the range of from about 2 to about 50 weight percent, more preferablyin the range of from about 5 to about 30 weight percent, and mostpreferably in the range of from 10 to 20 weight percent.

[0079] Once the promoter component has been distributed on, or with, theparticulated, calcined base support component, the desiredreduced-valence promoter component sorbent is prepared by drying theresulting composition under a drying condition as disclosed hereinfollowed by calcining under a calcining condition as disclosed herein tothereby provide dried, calcined, promoted particulates. The dried,calcined, promoted particulates are thereafter subjected to reductionwith a suitable reducing agent, preferably hydrogen or an appropriatehydrocarbon so as to produce a composition having a substantiallyreduced-valence promoter component content therein, preferably asubstantially zero content therein, with such zero valence promotercomponent being present in an amount sufficient to permit the removal ofsulfur from a hydrocarbon-containing fluid such as cracked-gasoline ordiesel fuel, according to the process disclosed herein.

[0080] A sorbent composition having a reduced-valence promoter componentof the present invention is a composition that has the ability to reactchemically and/or physically with sulfur. It is also preferable that thesorbent composition removes diolefins and other gum-forming compoundsfrom cracked-gasoline.

[0081] A sorbent composition having a reduced-valence promoter componentof the present invention comprises a promoter component that is in asubstantially reduced valence state, preferably a zero valence state.Preferably, the reduced-valence promoter component is reduced nickel.The amount of reduced-valence promoter component, preferably reducednickel, in a sorbent composition of the present invention is an amountwhich will permit the removal of sulfur from cracked-gasoline or dieselfuel. Such amounts of reduced-valence promoter component, preferablyreduced nickel or cobalt or a mixture of nickel and cobalt are generallyin the range of from about 1.0 to about 60 weight percent of the totalweight of the sorbent composition (support composition plus promoter).

[0082] In one presently preferred embodiment of the present invention,the reduced nickel is present in an amount in the range of from about 15to about 30 weight percent based on the total weight of the nickel andthe reduced nickel has been substantially reduced to zero valence.

[0083] In another presently preferred embodiment of the presentinvention, zinc oxide is present in an amount in the range of from about40 to about 80 weight percent zinc oxide based on the total weight ofthe sorbent support, expanded perlite is present in an amount in therange of from about 10 to about 30 weight percent expanded perlite basedon the total weight of the sorbent support, and alumina is present in anamount in the range of from about 1.0 to about 20 weight percent basedon the total weight of the sorbent support, and promoter metal ispresent prior to reduction in an amount in the range of from about 10 toabout 30 weight percent promoter metal based on the total weight of thecomposition.

[0084] During reduction of the oxidized sorbent particulates, it ispreferred for at least a portion of the substitutional solid metal oxidesolution (M_(X)Zn_(Y)O) found in the oxidized sorbent particulates to bereduced to form a substitutional solid metal solution characterized bythe formula: M_(A)Zn_(B), wherein M is the promoter metal, A is anumerical value in the range of from 0.01 to 0.99, and B is a numericalvalue in the range of from 0.01 to 0.99. In the above formula for thesubstitutional solid metal solution, it is preferred for A to be in therange of from about 0.50 to about 0.97, more preferably in the range offrom about 0.80 to about 0.95, and most preferably in the range of from0.90 to 0.94. It is further preferred for B to be in the range of fromabout 0.03 to about 0.50, more preferably in the range of from about0.05 to about 0.20, and most preferably in the range of 0.06 to 0.10.Preferably, B is equal to (1−A).

[0085] The reduced sorbent particulates preferably comprise thesubstitutional solid metal solution (M_(A)Zn_(B)) in an amount in therange of from about 5 to about 80 weight percent, more preferably in therange of from about 10 to about 60 weight percent, still more preferablyin the range of from about 20 to about 50 weight percent, and mostpreferably in the range of from 30 to 40 weight percent. The reducedsorbent particulates preferably comprise the promoter metal-zincaluminate (M_(Z)Zn_((1−Z))Al₂O₄), described above with reference to theoxidized (i.e., unreduced) sorbent particulates, in an amount in therange of from about 2 to about 50 weight percent, more preferably in therange of from about 5 to about 30 weight percent, and most preferably inthe range of from 10 to 20 weight percent. The reduced sorbentparticulates preferably comprise zinc oxide in an amount in the range offrom about 10 to about 90 weight percent, more preferably in the rangeof from about 20 to about 60 weight percent, and most preferably in therange of from 30 to 40 weight percent. The reduced sorbent particulatespreferably comprise perlite in an amount in the range of from about 2 toabout 50 weight percent, more preferably in the range of from about 5 toabout 30 weight percent, and most preferably in the range of from 10 to20 weight percent.

[0086] The sorbent compositions of the present invention, which areuseful in the desulfurization process of the present invention, can beprepared by a process comprising:

[0087] (a) mixing a support component preferably comprising zinc oxide,expanded perlite, and alumina, so as to form a mixture selected from thegroup consisting of a wet mix, a dough, a paste, a slurry, and the likeand combinations thereof;

[0088] (b) particulating, preferably spray-drying, the mixture to formparticulates selected from the group consisting of granules, extrudates,tablets, pellets, spheres, micro-spheres, and the like and combinationsthereof, preferably micro-spheres;

[0089] (c) drying the particulate under a drying condition as disclosedherein to form a dried particulate;

[0090] (d) calcining the dried particulate under a calcining conditionas disclosed herein to form a calcined particulate;

[0091] (e) incorporating, preferably impregnating, the calcinedparticulate with a promoter component thereof to form a promotedparticulate;

[0092] (f) drying the promoted particulate under a drying condition asdisclosed herein to form a dried, promoted particulate;

[0093] (g) calcining the dried, promoted particulate under a calciningcondition as disclosed herein to form a calcined, promoted particulate;and

[0094] (h) reducing the calcined, promoted particulate with a suitablereducing agent so as to produce a sorbent composition having areduced-valence promoter component content therein, preferably areduced-valence nickel content therein, and wherein the reduced-valencepromoter component content is present in an amount effective for theremoval of sulfur from a hydrocarbon-containing fluid such ascracked-gasoline or diesel fuel when such hydrocarbon-containing fluidis contacted with a sorbent composition(s) of the present inventionaccording to a process(es) of the present invention.

[0095] A process of using a novel sorbent composition(s) of the presentinvention to desulfurize a hydrocarbon-containing fluid, such ascracked-gasoline or diesel fuel, to provide a desulfurizedcracked-gasoline or diesel fuel comprises:

[0096] (a) desulfurizing, in a desulfurization zone, ahydrocarbon-containing fluid selected from the group consisting ofcracked-gasoline, diesel fuel, with a sorbent composition of the presentinvention;

[0097] (b) separating the desulfurized hydrocarbon-containing fluid fromthe resulting sulfurized sorbent composition;

[0098] (c) regenerating at least a portion of the sulfurized sorbentcomposition to produce a regenerated, desulfurized, sorbent composition;

[0099] (d) reducing at least a portion of the regenerated, desulfurized,sorbent composition to produce a reduced, regenerated, desulfurizedsorbent composition; and

[0100] (e) returning at least a portion of the reduced, regenerated,desulfurized sorbent composition to the desulfurization zone.

[0101] The desulfurizing step (a) of the present invention is carriedout under a set of conditions that includes total pressure, temperature,weight hourly space velocity, and hydrogen flow. These conditions aresuch that the sorbent composition can desulfurize thehydrocarbon-containing fluid to produce a desulfurizedhydrocarbon-containing fluid and a sulfurized sorbent composition.

[0102] In carrying out the desulfurization step of a process of thepresent invention, it is preferred that the cracked-gasoline or dieselfuel be in a gas or vapor phase. However, in the practice of the presentinvention, it is not essential that such hydrocarbon-containing fluid betotally in a gas or vapor phase.

[0103] The total pressure can be in the range of from about 15 poundsper square inch absolute (psia) to about 1500 psia. However, it ispresently preferred that the total pressure be in a range of from about50 psia to about 500 psia.

[0104] In general, the temperature should be sufficient to keep thehydrocarbon-containing fluid in essentially a vapor or gas phase. Whilesuch temperatures can be in the range of from about 100° F. to about1000° F., it is presently preferred that the temperature be in the rangeof from about 400° F. to about 800° F. when treating a cracked-gasoline,and in the range of from about 500° F. to about 900° F. when treating adiesel fuel.

[0105] Weight hourly space velocity (“WHSV”) is defined as the numericalratio of the rate at which a hydrocarbon-containing fluid is charged tothe desulfurization zone in pounds per hour at standard condition oftemperature and pressure (“STP”) divided by the pounds of sorbentcomposition contained in the desulfurization zone to which thehydrocarbon-containing fluid is charged. In the practice of the presentinvention, such WHSV should be in the range of from about 0.5 hr⁻¹ toabout 50 hr⁻¹, preferably in the range of from about 1 hr⁻¹ to about 20hr⁻¹.

[0106] In carrying out the desulfurizing step, it is presently preferredthat an agent be employed which interferes with any possible chemical orphysical reacting of the olefinic and aromatic compounds in thehydrocarbon-containing fluid which is being treated with the solidreduced metal containing sorbent composition. Preferably, such agent ishydrogen.

[0107] Hydrogen flow in the desulfurization zone is generally such thatthe mole ratio of hydrogen to hydrocarbon-containing fluid is the rangeof from about 0.1 to about 10, preferably in the range of from about 0.2to about 3.

[0108] The desulfurization zone can be any zone wherein desulfurizationof cracked-gasoline or diesel fuel can take place. Examples of suitablezones are fixed bed reactors, moving bed reactors, fluidized bedreactors, transport reactors, and the like. Presently, a fluidized bedreactor or a fixed bed reactor is preferred.

[0109] If desired, during the desulfurization of the cracked-gasoline ordiesel fuel, diluents such as methane, carbon dioxide, flue gas,nitrogen, and the like and combinations thereof can be used. Thus, it isnot essential to the practice of the present invention that a highpurity hydrogen be employed in achieving the desired desulfurization ofa hydrocarbon-containing fluid such as cracked-gasoline or diesel fuel.

[0110] It is presently preferred when utilizing a fluidized bed reactorsystem that a sorbent composition be used having a particle size in therange of from about 10 micrometers to about 1000 micrometers.Preferably, such sorbent composition should have a particle size in therange of from about 20 micrometers to about 500 micrometers, and, morepreferably, in the range of from 30 micrometers to 400 micrometers. Whena fixed bed reactor system is employed for the practice of adesulfurization process(s) of the present invention, the sorbentcomposition should generally have a particle size in the range of fromabout {fraction (1/32)} inch to about ½ inch diameter, preferably in therange of from about {fraction (1/32)} inch to about ¼ inch diameter.

[0111] It is further presently preferred to use a sorbent compositionhaving a surface area in the range of from about 1 square meter per gram(m²/g) to about 1000 square meters per gram of sorbent composition,preferably in the range of from about 1 m²/g to about 800 m²/g.

[0112] The separation of the desulfurized hydrocarbon-containing fluid,preferably gaseous or vaporized desulfurized cracked gasoline or dieselfuel and sulfurized sorbent composition, can be accomplished by anymanner known in the art that can separate a solid from a gas. Examplesof such means are cyclonic devices, settling chambers, impingementdevices for separating solids and gases, and the like and combinationsthereof. The desulfurized gaseous cracked-gasoline or desulfurizedgaseous diesel fuel, can then be recovered and preferably liquefied.Liquification of such desulfurized hydrocarbon-containing fluid can beaccomplished by any manner known in the art.

[0113] The gaseous cracked-gasoline or gaseous diesel fuel, suitable asa feed in a process(es) of the present invention is a composition thatcontains, in part, olefins, aromatics, sulfur, as well as paraffins andnaphthenes.

[0114] The amount of olefins in gaseous cracked-gasoline is generally inthe range of from about 10 to about 35 weight percent olefins based onthe total weight of the gaseous cracked-gasoline. For diesel fuel thereis essentially no olefin content.

[0115] The amount of aromatics in gaseous cracked-gasoline is generallyin the range of from about 20 to about 40 weight percent aromatics basedon the total weight of the gaseous cracked-gasoline. The amount ofaromatics in gaseous diesel fuel is generally in the range of from about10 to about 90 weight percent aromatics based on the total weight of thegaseous diesel fuel.

[0116] The amount of sulfur in the hydrocarbon-containing fluid, i.e.cracked-gasoline or diesel fuel, suitable for use in a process of thepresent invention can be in the range of from about 100 parts permillion sulfur by weight of the cracked-gasoline to about 10,000 partsper million sulfur by weight of the cracked-gasoline and from about 100parts per million sulfur by weight of the diesel fuel to about 50,000parts per million sulfur by weight of the diesel fuel prior to thetreatment of such hydrocarbon-containing fluid with a desulfurizationprocess(es) of the present invention.

[0117] The amount of sulfur in the desulfurized cracked-gasoline ordesulfurized diesel fuel, following treatment in accordance with adesulfurization process of the present invention, is less than about 100parts per million (ppm) sulfur by weight of hydrocarbon-containingfluid, preferably less than about 50 ppm sulfur by weight ofhydrocarbon-containing fluid, and more preferably less than about 5 ppmsulfur by weight of hydrocarbon-containing fluid.

[0118] In carrying out a process of the present invention, if desired, astripper unit can be inserted before and/or after the regeneration ofthe sulfurized sorbent composition. Such stripper will serve to remove aportion, preferably all, of any hydrocarbon from the sulfurized sorbentcomposition. Such stripper can also serve to remove oxygen and sulfurdioxide from the system prior to introduction of the regenerated sorbentcomposition into the sorbent activation zone (i.e., sorbent reductionzone). The stripping comprises a set of conditions that includes totalpressure, temperature, and stripping agent partial pressure.

[0119] Preferably, the total pressure in a stripper, when employed, isin the range of from about 25 pounds per square inch absolute (psia) toabout 500 psia.

[0120] The temperature for such stripping can be in the range of fromabout 100° F. to about 1000° F.

[0121] The stripping agent is a composition that helps to remove ahydrocarbon(s) from the sulfurized sorbent composition. Preferably, thestripping agent is nitrogen.

[0122] The sorbent regeneration zone employs a set of conditions thatincludes total pressure and sulfur removing agent partial pressure.Total pressure is generally in the range of from about 25 pounds persquare inch absolute (psia) to about 500 psia.

[0123] The sulfur removing agent partial pressure is generally in therange of from about 1 percent to about 25 percent of the total pressure.

[0124] The sulfur removing agent is a composition that helps to generategaseous sulfur-containing compounds and oxygen-containing compounds suchas sulfur dioxide, as well as to bum off any remaining hydrocarbondeposits that might be present. The preferred sulfur removing agentsuitable for use in the sorbent regeneration zone is selected fromoxygen-containing gases such as air.

[0125] The temperature in the sorbent regeneration zone is generally inthe range of from about 100° F. to about 1500° F., preferably in therange of from about 800° F. to about 1200° F.

[0126] The sorbent regeneration zone can be any vessel wherein thedesulfurizing or regeneration of the sulfurized sorbent composition cantake place.

[0127] The desulfurized sorbent composition is then reduced in anactivation zone with a reducing agent so that at least a portion of thepromoter component content of the sorbent composition is reduced toproduce a solid reduced-valence promoter component to permit the removalof sulfur from a cracked-gasoline or diesel fuel according to theinventive process disclosed herein.

[0128] In general, when practicing the present invention, theactivation, i.e., reduction, of the desulfurized sorbent composition iscarried out at a temperature in the range of from about 100° F. to about1500° F. and at a pressure in the range of from about 15 pounds persquare inch absolute (psia) to about 1500 psia. Such reduction iscarried out for a time sufficient to achieve the desired level ofpromoter component reduction contained in the skin of the sorbentcomposition. Such reduction can generally be achieved in a time periodin the range of from about 0.01 hour to about 20 hours.

[0129] Following the activation, i.e., reduction, of the regeneratedsorbent composition, at least a portion of the resulting activated(i.e., reduced) sorbent composition can be returned to thedesulfurization zone.

[0130] When carrying out the process of the present invention, the stepsof desulfurization, regeneration, activation (i.e., reduction), andoptionally stripping before and/or after such regeneration can beaccomplished in a single zone or vessel or in multiple zones or vessels.

[0131] When carrying out the process of the present invention in a fixedbed reactor system, the steps of desulfurization, regeneration,activation, and optionally stripping before and/or after suchregeneration are accomplished in a single zone or vessel.

[0132] The desulfurized cracked-gasoline can be used in the formulationof gasoline blends to provide gasoline products suitable for commercialconsumption and can also be used where a cracked-gasoline containing lowlevels of sulfur is desired.

[0133] Desulfurized cracked-gasoline products made in accordance withthis invention are novel and unique desulfurized cracked-gasolines, havevery low sulfur content levels and generally comprise only two differentclasses of sulfur species, thiophenes and benzothiophenes. Generally,the sulfur content of cracked-gasolines produced in accordance with thisinvention can be less than about 25 parts per million by weight (ppmw),preferably less than about 15 ppmw and most preferably, less than about10 ppmw sulfur.

[0134] In addition to having very low sulfur content, the desulfurizedcracked-gasoline produced in accordance with the present invention hasless than about 1 parte per million by weight (ppmw), preferably lessthan about 0.5 ppmw, and most preferably less than about 0.1 ppmw thiolcompounds. Additionally, desulfurized cracked-gasolines produced inaccordance with this invention also have less than about 1 ppm,preferably less than about 0.5 ppmw, and most preferably less than about0.1 ppmw tetrahydrothiophenes. Further, desulfurized-cracked gasolinesproduced in accordance with the present invention have less than about 1ppm, preferably less than about 0.7 ppm, and most preferably less thanabout 0.5 ppmw dihydrobenzothiophene compounds. Desulfurized gasoline,desulfurized in accordance with other methods known in the art, such as,for example hydrotreating, showed the presence of many different typesof sulfur. These types of sulfur compounds include thiols, thiophenes,tetrahydrothiophenes, benzothiophenes, and dihydrobenzothiophenes.

[0135] Sulfur-containing compounds, as used in this disclosure, aredefined as generally used in common chemical usage. Generally, as usedin this disclosure, thiols, or mercaptans, are sulfur-containingcompounds defined by the formulae of R-SH. Thiophenes are five-memberedcyclic sulfur-containing compounds comprising a ring of four carbonatoms and one sulfur atom, having a general formulae of (CR)₄S.Benzothiophenes are cyclic sulfur-containing compounds comprising asix-membered ring and a four-membered ring, wherein a sulfur atom is inthe five-membered ring, and having a general formulae of C₆R₄.S.CR:CR,wherein the six-membered ring and five-membered ring are attached andeach ring has two carbon atoms in common. For all of these compounds, Rcan be the same or different and is selected from the group consistingof hydrogen or a hydrocarbyl radical radical selected from the groupconsisting of alkyl, alkenyl, aryl, alkyaryl, or arylalkyl radicalshaving from about 1 to about 20 carbon atoms per group.

[0136] In addition to the absence of thiols and tetrahydrothiophenes andminimal levels of dihydrobenzothiophenes in desulfurizedcracked-gasolines made in accordance with the present invention, theoctane number of the inventive desulfurized cracked-gasolines is reducedminimally, especially in comparison to other desulfurization processes.Other desulfurization processes, such as, for example hydrotreating, canreduce the average octane number, as defined by Δ(RON+MON+MON)/2, by anamount that is significant and detrimental to end users of the gasolineproducts. Desulfurized cracked-gasolines produced in accordance with thepresent invention have an octane loss, or octane reduction in to averageoctane number by less than about 3.5, preferably less than about 3, andmost preferably less than about 2 octane numbers. Desulfurizedcracked-gasolines produced in accordance with the present invention,which have low sulfur content and either retain a similar octane contentor have minimal octane loss when compared to gasolines that has not beendesulfurized in accordance with the present invention can beenvironmentally friendly, beneficial to catalytic converters invehicles, such as, for example automobiles, and can maintain vehicle gasmileage.

[0137] The desulfurized diesel fuel can be used in the formulation ofdiesel fuel blends to provide diesel fuel products.

EXAMPLES

[0138] The following examples are intended to be illustrative of thepresent invention and to teach one of ordinary skill in the art to makeand use the invention. These examples are not intended to limit theinvention in any way.

Example I

[0139] A solid reduced nickel sorbent system was produced by mixing 10%alumina (Vista Dispal), 40% diatomaceous earth (World Chemical), and 50%zinc oxide with water at 42% solids using tetra sodium pyrophosphate(TSPP) as the dispersing agent.

[0140] The resulting slip was spray dried using a Niro Mobil Minor SprayDrier fitted with a 0.035 inch air cap and a 0.35 inch fountain headnozzle. The inlet temperature was 320° C. and the outlet temperature was150° C. Air flow through the nozzle was 70 liters per minute. The slipwas delivered at approximately 43 cc/min H₂O.

[0141] The spray dried product was dried in air using a muffle furnaceat a temperature of 150° C. for 1 hour and then calcined at atemperature of 635° C. for a period of 1 hour.

[0142] The resulting calcined composition was screened to remove fines<40 microns and oversized particles of >250 microns.

[0143] The screened sorbent was impregnated with 12% nickel (as themetal) using melted nickel nitrate hexahydrate in 5% water to get it tomelt/dissolve. The resulting solution was then sprayed onto the sorbentusing a Sono-Tec sprayer while the sorbent particles were rotated in abaffled cement mixer type drum. The nickel impregnated sorbent was againcalcined at a temperature of 635° C. for 1 hour.

[0144] The calcined 12% nickel sorbent composition was again impregnatedwith 15% nickel as carried out supra.

[0145] The resulting 27% nickel impregnated sorbent was then calcined ata temperature of 635° C. for a period of 1 hour to provide a 30% (byweight) of a nickel impregnated sorbent system.

[0146] The resulting impregnated sorbent system has a Davison attritionresistance value of 19.26.

Example II

[0147] 10 grams of the sorbent as prepared in Example I were placed in a½ inch diameter quartz tube having a length of about 12 inches andhaving a glass frit positioned above the lower ⅓ thereof so as toprovide an inert support for the bed of sorbent which was placedthereon.

[0148] During each cycle, gaseous cracked-gasoline was pumped upwardlythrough the reactor at a rate of 13.6 ml per hour. The gaseouscracked-gasoline had a motor octane number of 80.6 (MON) or a researchoctane number of 92.1 (RON), an olefin content of 21.2 weight percent,340 parts per million sulfur by weight sulfur-containing compounds basedon the total weight of the gaseous cracked-gasoline and about 0.03weight percent thiophenic compounds based on the weight ofsulfur-containing compounds in the gaseous cracked-gasoline.

[0149] During each cycle, the reactor was maintained at a temperature of700° F. and a pressure of 15 pounds per square inch absolute (psia).Hydrogen flow was at 150 standard cubic centimeters per minute (sccm)diluted with 150 sccum of nitrogen.

[0150] Before cycle 1 was initiated, the sorbent was reduced withhydrogen flowing at a rate of 300 sccm at a temperature of 700° F. for aperiod of one hour. Each cycle consisted of four hours with the productsulfur (ppm) for each cycle measured at one hour intervals over eachfour-hour cycle period. After each cycle, the sorbent was regenerated at900° F. for two hours with a mixture of oxygen and nitrogen containingfour volume percent oxygen, then purged with nitrogen (regeneration),and then reduced in hydrogen flowing at a rate of 300 cc for one hour at700° F. (activation).

[0151] The sorbent compositions were each tested over 2 cycles. Eachcycle utilized a mixture of 150 sccm hydrogen and 150 sccm nitrogen and350 sccm/hydrocarbon.

[0152] The following results were obtained: Cycle 1 2 PPM Sulfur 10 5PPM Sulfur 20 20 PPM Sulfur 25 15 PPM Sulfur 20 15

Example III

[0153] A solid reduced nickel sorbent system was produced by mixing13.75% alumina (nitric acid peptized Condea Disperal), 17.25% milledexpanded perlite (R/F 27M), and 69% zinc oxide with water at 42% solidsusing ammonium polyacrylate as the dispersing agent.

[0154] The resulting slip was spray dried using a Niro Mobil Minor SprayDrier fitted with a 0.035 inch air cap and a 0.35 inch fountain headnozzle. The inlet temperature was 320° C. and the outlet temperature was150° C. Air flow through the nozzle was 70 liters per minute. The slipwas delivered at approximately 43 cc/min H₂O.

[0155] The spray dried product was dried in air using a muffle furnaceat a temperature of 150° C. for 1 hour and then calcined at atemperature of 635° C. for a period of 1 hour.

[0156] The resulting calcined composition was screened to remove fines<40 microns and oversized particles of >250 microns.

[0157] The screened sorbent was impregnated with 15% nickel (as themetal) using melted nickel nitrate hexahydrate in 5% water to get it tomelt/dissolve. The resulting solution was then sprayed onto the sorbentusing a Sono-Tec sprayer while the sorbent particles were rotated in abaffled cement mixer type drum. The nickel impregnated sorbent was againcalcined at a temperature of 635° C. for 1 hour.

[0158] One half of the resulting calcined 15% nickel sorbent compositionwas again impregnated with 15% nickel as carried out supra.

[0159] The resulting 30% nickel impregnated sorbent was then calcined ata temperature of 635° C. for a period of 1 hour to provide a 30% (byweight) of a nickel impregnated sorbent system.

[0160] The resulting impregnated sorbent system has a Davison attritionresistance value of 10.

Example IV

[0161] 10 grams of each of the sorbents as prepared in Example III (15%and 30% nickel) were separately placed in ½ inch diameter quartz tubeshaving a length of about 12 inches and having a glass frit positionedabove the lower ⅓ thereof so as to provide an inert support for the bedof sorbent which was placed thereon in each of the quartz tubes.

[0162] During each cycle, gaseous cracked-gasoline was pumped upwardlythrough the reactor at a rate of 13.6 ml per HR. The gaseouscracked-gasoline had a motor octane number of 80.6 (MON) or a researchoctane number of 92.4 (RON), an olefin content of 21.2 weight percent,340 parts per million sulfur by weight sulfur containing compound basedon the total weight of the gaseous cracked-gasoline and about 0.03weight percent thiophenic compounds based on the weight ofsulfur-containing compounds in the gaseous cracked-gasoline.

[0163] During each cycle, the reactor was maintained at a temperature of700° F. and a pressure of 15 pounds per square inch absolute (psia).Hydrogen flow was at 150 standard cubic centimeters per minute (sccm)diluted with 150 sccm of nitrogen.

[0164] Before cycle 1 was initiated, the sorbent was reduced withhydrogen flowing at a rate of 300 sccm at a temperature of 700° F. for aperiod of one hour. Each cycle consisted of four hours with the productsulfur (ppm) for each cycle measured at one hour intervals over eachfour-hour cycle period. After each cycle, the sorbent was regenerated at900° F. for two hours with a mixture of oxygen and nitrogen containingfour volume percent oxygen, then purged with nitrogen (regeneration) andthen reduced in hydrogen flowing at a rate of 300 cc for one hour at700° F. (activation).

[0165] The following results were obtained: TABLE 1 PPM Sulfur inCracked-Gasoline Using 15% Ni Sorbent System Cycle 1 2 3 4 5 ppm sulfur5 5 10 <5 5 ppm sulfur 5 5 5 <5 <5 ppm sulfur 5 5 10 10 <5 ppm sulfur <5<5

[0166] TABLE 2 PPM Sulfur in Cracked-Gasoline Using 30% Ni SorbentSystem Sorption Cycle 1 2 3 4 5 ppm sulfur <5 <5 <5 5 <5 ppm sulfur <5<5 10 5 5 ppm sulfur <5 5 <5 <5 5

[0167] The above data clearly demonstrate that the sorbent system of thepresent invention provides a system for the ready removal of sulfur froma hydrocarbon containing fluid such as cracked-gasoline.

[0168] In addition, due to the low Davison attrition value of thesorbent systems of Example III, there is provided an operable sorbentsystem which is attrition resistant and thus capable of extended useprior to the need for replacement of same.

[0169] Use of the milled expanded perlite in the formation of thesorbent systems of Example III provided a sorbent composition which hasonly two thirds the packing density of the sorbent system of Example I,and thus takes only two thirds the weight to fill the same volume.Moreover, the majority of the pore volume of the resulting compositionwas as macropores which in turn provided a system most suitable for theremoving of gasoline sulfur.

Example V

[0170] A solid reduced nickel sorbent system was produced by combining175.9 pounds of deionized water and 28.3 pounds of alumina (VistaDispal™) in a mixer. The water/alumina slurry was mixed until thealumina was peptized. In a separate mixer, 27.4 pounds of milledexpanded perlite (R/F 27M) was dry-blended with 104.8 pounds of powderedzinc oxide. The perlite/ZnO dry mixture was slowly added to thewater/alumina slurry while mixing was continued. The resulting supportmixture was mixed until homogeneous.

[0171] The support mixture was then spray dried in a 33 foot spray drierhaving a wheel atomizer which spun at 9,000 RPM. The air charged to thespray drier during drying had an inlet temperature of about 500° F. andan outlet temperature of about 280° F. The microspherical supportparticulates produced by spray drying were then dried at about 250° F.for about 3 hours and calcined on a belt calciner at a temperature ofabout 635° C. for about 1.5 hours.

[0172] The calcined support particulates were then sieved to removeoversized particles (larger than 100 mesh) and fine particles (smallerthan 635 mesh). The sieved support particulates were then placed in abaffled cement mixer-type mixer and impregnated with nickel by sprayingan aqueous solution of nickel nitrate hexahydrate on the supportparticulates while the mixer was rotated. The material was thendischarged from the mixer and dried at 250° F. for about 8 hours, thencalcined on a belt calciner at 635° C. for 1.5 hours. The calcined(i.e., oxidized) promoted sorbent particulates were then sieved toremove oversized particles (larger than 100 mesh) and fine particles(smaller than 635 mesh).

[0173] A portion of the resulting calcined (i.e., oxidized) promotedsorbent was charged to a fixed fluidized bed 1 inch I.D. quartz reactor.The sorbent in the reactor was then reduced in hydrogen flowing at 300sccm at 750° F. for 1 hour. The reduced promoted sorbent was then cooledwith nitrogen and removed from the reactor.

Example VI

[0174] Samples of the calcined unpromoted support, oxidized promotedsorbent, and reduced promoted sorbent, prepared in Example V, wereanalyzed using X-ray diffraction and Phase Filtering (R. V. Siriwardane,J. A. Poston, G. Evans, Jr. Ind. Eng. Chem. Res. 33 (1994) 2810-2818),an adapted form of Rietveld modeling (RIQAS rietveld analysis, OperatorsManual, Material Data, Inc., Berkley, Calif. (1999)). All X-raydiffraction measurements were taken using a Philips XRG 3100 generatorequipped with a long fine focus copper X-ray source powered at 40 kV &30 mA; Philips 3020 digital goniometer & Philips 3710 MPD controlcomputer; and a Kevex PSI Peltier cooled silicon detector. The Kevexdetector was operated with a Kevex 4601 ion pump controller, Kevex 4608Peltier current supply, Kevex 4621 detector bias, Kevex 4561A pulseprocessor, and Kevex 4911-A single channel analyzer.

[0175] Diffraction patterns were acquired using Philips APD version 4.1csoftware. All Rietveld calculations were performed using Material Data,Inc. Riqas version 3.1c software (Outokumpu HSC Chemistry for Windows:Users Guide, Outokumpo Research Oy, Pori, Finland (1999)). The programswere run under the MS Windows® 95 operating system using an IntelPentium® III 300 MHz class personal computer equipped with 128 MB ofRAM.

[0176] The X-ray diffraction analysis of the calcined unpromoted supportindicated that it contained the following components in the followingamounts:

[0177] Zinc Oxide (ZnO): 70.3 wt. %

[0178] Zinc Aluminate (ZnAl₂O₄): 14.9 wt. %

[0179] Perlite: 14.8 wt. %.

[0180] The X-ray diffraction analysis of the oxidized promoted sorbentindicated that it contained the following components in the followingamounts:

[0181] Zinc Oxide (ZnO): 40.0 wt. %

[0182] Perlite: 13.5 wt. %

[0183] Zinc Aluminate Substitutional Solid Solution(Ni_(Z)Zn_((1−Z))Al₂O₄): 15.2 wt. %

[0184] Nickel Zinc Oxide Substitutional Solid Solution(Ni_(0.7)Zn_(0.3)O): 31.2 wt. %. The X-ray diffraction analysis of thereduced promoted sorbent indicated that it contained the followingcomponents in the following amounts:

[0185] Zinc Oxide (ZnO): 36.9 wt. %

[0186] Perlite: 13.1 wt. %

[0187] Nickel Zinc Aluminate Substitutional Solid Solution

[0188] (Ni_(Z)Zn_((1−Z))Al₂O₄): 15.9 wt. %

[0189] Nickel Zinc Metal Substitutional Solid Solution(Ni_(0.92)Zn_(0.08)): 34.1 wt. %.

Example VII

[0190] Examples VII-IX demonstrate the effects upon product compositionof treating a gasoline sample using the S Zorb process compared toconventional hydrotreating. They are intended to be illustrative of thepresent invention and to teach one of ordinary skill in the art to makeand use the invention. These examples are not intended to limit theinvention in any way.

[0191] A catalytic-cracked refinery gasoline blend was used for thesetests. The feed contained about 18 weight percent olefins and 34 weightpercent aromatics (PIONA gas chromatography method based on ASTM D-5443)and had a motor octane number (MON) of 79.9 and a research octane number(RON) of 89.8 as determined by engine tests. Total sulfur was measuredusing a sulfur fluorescence method, ASTM D-5453. Sulfur species weredetermined by a modified ASTM D-5623 gas chromatography method using asulfur chemiluminescent detector. The specific sulfur species wereidentified by using external standards as well as by the sequentialextractions of mercaptans and sulfides. Table 3 summarizes the sulfuranalytical results. TABLE 3 Sulfur Distribution In ppm By Weight ForCatalytic-Cracked Refinery Gasoline Blend Sulfur Species Amount (ppm)Total 1400 Thols 23 Thiophenes 484 Tetrahydrothiophenes 49Benzothiophenes 796 Dihydrobenzothiophenes 43 Other 5

Example VIII

[0192] The feed described in Example I was hydrotreated over a Co/MoTK-554 distillate hydrotreating catalyst commercially available fromHaldor-Topsoe. The run was performed in a downflow reactor over 25 cc ofdried catalyst mixed with 50 cc of 30/40 grit alundum at 500 SCF/Bblhydrogen, 2.0 liquid hourly space velocity, and 100 psi pressure. Thecatalyst was presulfided at atmospheric pressure using a 10% hydrogensulfide in hydrogen mixture with flow rate of 190 cc/min. Thetemperature was 400° F. for ten hours, followed by two hours at each 50°F. increment between 400 and 700° F., and finally for four hours at 700°F. The hydrotreating temperature was varied from 500 to 580° F. toachieve sulfur removal ranging from 87 to 99 weight percent. Afterhydrotreatment, samples were collected and distribution of sulfur in theproduct was determined. These results are given in Table II. Enginetests were used to determine the change in average octane number,Δ(RON+MON)/2, for the 525, 560, and 580° F. hydrotreated samplescompared to the feed (also given in Table II). TABLE 4 Sulfurdistribution in product (ppm by weight) after hydrotreating Property ppmsulfur ppm sulfur ppm sulfur ppm sulfur Measured (525° F.) (540° F.)(560° F.) (580° F.) Total Sulfur 61 36 21 13 Thiols 20.7 10.4 8.1 4.0Thiophenes 20.9 12.7 3.1 3.5 Tetrahydrothiophenes 12.3 6.6 6.6 2.8Benzothiophenes 3.8 4.1 2.6 2.1 Dihydrobenzo- 0.5 <0.1 <0.1 <0.1thiophenes Other 2.6 1.9 0.6 0.6 Δ(RON + MON)/ 2 −3.8 not −5.6 −6.2determined

Example IX

[0193] A sorbent consisting of nickel supported on zinc oxide, alumina,and perlite was prepared by the following method. Zinc oxide was addedto expanded perlite in nitric acid solution and mixed for 15 minutes.(Perlite is commercially available from Silbrico Corp, Sil-Kleer R/F27M). Alumina (nitric acid peptized Condea Dispersal) was then mixedwith water and added to the zinc oxide and perlite slurry. After mixingfor 20 minutes, this material was spray dried, then heated to 150° C.and held there for one hour, and then heated to 635° C. and held therefor one hour. The spray-dried support contained 20.1 weight percentperlite, 16.8 weight percent alumina, and 63.1 weight percent zincoxide. It was then impregnated with 16 weight percent nickel nitratehexahydrate, heated to 150° C. and held there for one hour, and heatedto 635° C. and held there for one hour.

[0194] The sorbent described above was tested for its ability to removesulfur. Ten grams of the calcined sorbent were placed in a ½ inchdiameter steel tube having a length of about 11 inches and having asintered metal frit positioned above the lower one-third so as toprovide an inert support for the bed of sorbent.

[0195] Before reaction, the sorbent was reduced with hydrogen flowing ata rate of 1.0 standard cubic feet per hour (SCFH) at a temperature of850° F. for a period of two hours. Such conditions are hereinafterreferred to as “reducing conditions.”

[0196] During each reaction cycle, the reactor was maintained at atemperature of 750° F. and a pressure of 150 psig. Hydrogen flow was0.36 standard cubic feet per hour. Gaseous feed was pumped upwardlythrough the reactor at a rate of 106.4 ml per hour. Such conditions arehereinafter referred to as “reaction conditions.” Each reaction cycleconsisted of six hours, and there was capability of determining theproduct sulfur at any point during this time.

[0197] After completion of the first reaction cycle, sorbent was flushedwith nitrogen for thirty minutes at flow rate of 1.0 SCFH whiletemperature was increased to 900° F. The temperature was kept at 900° F.where the sorbent was regenerated under 0.5 SCFH air and 0.5 SCFHnitrogen for one hour, and then 1.0 SCFH of air for one hour. Suchconditions are hereinafter referred to as “regeneration conditions.”

[0198] The temperature was then decreased to 850° F. and the samplepurged with nitrogen for 30 minutes at a flow rate of 1.0 SCFH. Cycle 2began, like Cycle 1 under reducing conditions; i.e., treatment withhydrogen flowing at a rate of 1.0 standard cubic feet per hour (SCFH) ata temperature of 850° F. for a period of two hours.

[0199] The sorbent was tested over nine cycles. During the tenth cycle,product samples were collected and analyzed. The results in Table 5 wereobtained where the sulfur values given are the parts per million byweight in the product after the second hour, third hour, fourth, andfifth hour of treatment during cycle 10, respectively.

[0200] A gas chromatographic method, based on an PIONA analyses, wasused to calculate the change in average octane number, Δ(RON+MON)/2, forthe samples collected after the second, third, fourth, and sixth hour(Table 5). These octane number changes are significantly less, at thesame level of sulfur removal, than those obtained using conventionalhydrotreating (Table 4). TABLE 5 Sulfur distribution in produce (ppm byweight) after S Zorb Treatment ppm ppm ppm ppm ppm Propery sulfur sulfursulfur sulfur sulfur Measured Hour 2 Hour 3 Hour 4 Hour 5 Hour 6 Total.5 13.2 50.5 103 146 Thiols <0.1 <0.1 <0.1 <0.1 <0.1 Thiophenes 0.6 5.125.5 55.4 84.3 Tetrahydro- <0.1 <0.1 <0.1 <0.1 <0.1 tiophenesBenzothiophenes 4.5 7.9 25.0 47.5 61.4 Dihydrobenzo- <0.1 <0.1 <0.1 <0.1<0.1 thiophenes Other 0.4 0.2 <0.1 <0.1 <0.1 Δ(Ron + −1.8 −1.2 −0.8 not−0.5 MON)/2 determined

[0201] A comparison of Table 4 with Table 5 clearly teach that there aresignificant differences, in addition to the effects upon octane number,between the composition of the S Zorb treated and the hydrotreatedproducts. In particular, the S Zorb treated products contain only twodifferent classes of sulfur species—thiophenes and benzothiophenes. Thehydrotreated products, on the other hand, show the additional presenceof thiols and tetrahydrothiophenes. While not wishing to be bound bytheory, it is believed that thiols, which are most likely produced bythe reaction of hydrogen sulfide with olefins, can often be eliminatedby post-treatment. Tetrahydrothiophenes, however, cannot be readilyeliminated from hydrotreated gasoline samples.

[0202] Reasonable variations, modifications, and adaptations can be madewithin the scope of this disclosure and the appended claims withoutdeparting from the scope of this invention.

That which is claimed is:
 1. A sorbent composition suitable for removalof elemental sulfur and sulfur compounds from cracked-gasolines anddiesel fuels which is comprised of: (a) zinc oxide; (b) expandedperlite; (c) an aluminate; and (d) a promoter metal wherein saidpromoter metal is present in an amount which will effect the removal ofsulfur from a stream of cracked-gasoline or diesel fuel when contactedwith the same under desulfurization conditions and at least a portion ofsaid promoter metal is present in a zero valence state.
 2. A sorbentcomposition in accordance with claim 1 wherein said promoter metal is atleast one metal selected from the group consisting of nickel, cobalt,iron, manganese, copper, zinc, molybdenum, tungsten, silver, antimony,and vanadium.
 3. A sorbent composition in accordance with claim 2wherein said promoter metal is present in an amount in the range ofabout 1.0 to about 60 weight percent.
 4. A sorbent composition inaccordance with claim 4 wherein said zinc oxide is present in an amountin the range of about 10 to about 90 weight percent and said expandedperlite is present in an amount in the range of about 10 to about 40weight percent.
 5. A sorbent composition in accordance with claim 1wherein said promoter metal is nickel.
 6. A sorbent composition inaccordance with claim 1 wherein said promoter metal is cobalt.
 7. Asorbent composition in accordance with claim 1 wherein said promotermetal is a mixture of nickel and cobalt.
 8. A sorbent composition inaccordance with claim 1 wherein said aluminate comprises said promotermetal.
 9. A sorbent composition in accordance with claim 8 wherein saidpromoter metal is at least one metal selected from the group consistingof nickel, cobalt, iron, manganese, copper, zinc, molybdenum, tungsten,silver, antimony, and vanadium.
 10. A sorbent composition in accordancewith claim 9 wherein said promoter metal is nickel.
 11. A sorbentcomposition in accordance with claim 1 wherein said aluminate compriseszinc.
 12. A sorbent composition in accordance with claim 8 wherein saidaluminate comprises zinc.
 13. A sorbent composition in accordance withclaim 9 wherein said aluminate comprises zinc.
 14. A sorbent compositionin accordance with claim 10 wherein said aluminate comprises zinc.
 15. Asorbent composition suitable for removal of elemental sulfur and sulfurcompounds from cracked-gasolines and diesel fuels which is comprised of:(a) zinc oxide; (b) expanded perlite; and (c) a substitutional solidmetal solution of a promoter metal and zinc wherein said substitutionalsolid metal solution is present in an amount which will effect theremoval of sulfur from a stream of cracked-gasoline or diesel fuel whencontacted with the same under desulfurization conditions and at least aportion of said substitutional solid metal solution is present in a zerovalence state.
 16. A sorbent composition in accordance with claim 15wherein said promoter metal is at least one metal selected from thegroup consisting of nickel, cobalt, iron, manganese, copper, zinc,molybdenum, tungsten, silver, antimony, and vanadium.
 17. A sorbentcomposition in accordance with claim 16 wherein said promoter metal ispresent in an amount in the range of about 1.0 to about 60 weightpercent.
 18. A sorbent composition in accordance with claim 17 whereinsaid zinc oxide is present in an amount in the range of about 10 toabout 90 weight percent and said expanded perlite is present in anamount in the range of about 10 to about
 40. 19. A sorbent compositionin accordance with claim 15 wherein said promoter metal is nickel.
 20. Asorbent composition in accordance with claim 15 wherein said promotermetal is cobalt.
 21. A sorbent composition in accordance with claim 15wherein said promoter metal is a mixture of nickel and cobalt.
 22. Asorbent composition comprising: (a) zinc oxide; (b) a substitutionalsolid metal solution of a promoter metal and zinc wherein saidsubstitutional solid metal solution is present in an amount which willeffect the removal of sulfur from a stream of cracked-gasoline or dieselfuel when contacted with the same under desulfurization conditions, atleast a portion of said substitutional solid metal solution is presentin a zero valence state, and said promoter metal is at least one metalselected from the group consisting of nickel, cobalt, iron, manganese,copper, zinc, molybdenum, tungsten, silver, antimony, and vanadium. 23.A sorbent composition in accordance with claim 22 wherein said promotermetal is present in an amount in the range of about 1.0 to about 60weight percent and said zinc oxide is present in an amount in the rangeof about 10 to about 90 weight percent.
 24. A sorbent composition inaccordance with claim 23 further comprising expanded perlite in anamount in the range of 10 to about 40 weight percent.
 25. A sorbentcomposition in accordance with claim 24 wherein said promoter metal isnickel.
 26. A sorbent composition in accordance with claim 24 whereinsaid promoter metal is cobalt.
 27. A sorbent composition in accordancewith claim 24 wherein said promoter metal is a mixture of nickel andcobalt.
 28. A sorbent composition comprising: (a) zinc oxide; and (b) apromoter metal-zinc aluminate substitutional solid solutioncharacterized by the formula M_(Z)Zn_((1−Z))Al₂O₄ wherein M is apromoter metal selected from the group consisting of nickel, cobalt,iron, manganese, copper, zinc, molybdenum, tungsten, silver, antimony,and vanadium and Z is a numerical value in the range of from 0.01 to0.99.
 29. A sorbent composition in accordance with claim 28 wherein saidpromoter metal is nickel.
 30. A sorbent composition in accordance withclaim 28 further comprising a substitutional solid metal solution ofsaid promoter metal and zinc.
 31. A sorbent composition in accordancewith claim 30 wherein said promoter metal is nickel.
 32. A sorbentcomposition in accordance with claim 28 further comprising expandedperlite.
 33. A sorbent composition in accordance with claim 32 whereinsaid zinc oxide is present in an amount in the range of about 10 toabout 90 weight percent and said expanded perlite is present in anamount in the range of about 10 to about 40 weight percent.
 34. Asorbent composition in accordance with claim 33 wherein said promotermetal is nickel.
 35. An oxidized sorbent composition comprising: (a)zinc oxide; and (b) a substitutional solid metal oxide solution whereinsaid substitutional solid metal oxide solution is characterized by theformula M_(X)Zn_(Y)O, wherein M is a promoter metal and X and Y are eachnumerical values in the range of from 0.01 to 0.99.
 36. An oxidizedsorbent composition in accordance with claim 35 wherein X is in therange of about 0.50 to about 0.90 and Z is in the range of about 0.10and 0.50.
 37. An oxidized sorbent composition in accordance with claim36 wherein M is a metal selected from the group consisting of nickel,cobalt, iron, manganese, copper, zinc, molybdenum, tungsten, silver,antimony, and vanadium.
 38. An oxidized sorbent composition inaccordance with claim 35 wherein X is in the range of about 0.60 andabout 0.80 and Y is equal to about (1−X).
 39. An oxidized sorbentcomposition in accordance with claim 38 wherein M is nickel.
 40. Anoxidized sorbent composition in accordance with claim 35 wherein saidzinc oxide is present in an amount in the range of about 10 to about 90weight percent and said substitutional solid metal oxide solution ispresent in an amount in the range of about 5 to about 70 weight percent.41. An oxidized sorbent composition in accordance with claim 35 furthercomprising a promoter metal-zinc aluminate substitutional solid solutioncharacterized by the formula M_(Z)Zn_((1−Z))Al₂O₄, wherein M is saidpromoter metal and Z is a numerical value in the range of from 0.01 to0.99.
 42. An oxidized sorbent composition in accordance with claim 41wherein M is a metal selected from the group consisting of nickel,cobalt, iron, manganese, copper, zinc, molybdenum, tungsten, silver,antimony, and vanadium.
 43. An oxidized sorbent composition inaccordance with claim 41 wherein M is nickel.
 44. An oxidized sorbentcomposition in accordance with claim 41 wherein said zinc oxide ispresent in an amount in the range of about 10 to about 90 weightpercent, said substitutional solid metal oxide solution is present in anamount in the range of about 5 to about 70 weight percent, and saidpromoter metal-zinc aluminate substitutional solid solution is presentin an amount in the range of about 2 to about 50 weight percent.
 45. Anoxidized sorbent composition in accordance with claim 35 furthercomprising expanded perlite.
 46. An oxidized sorbent composition inaccordance with claim 40 further comprising expanded perlite in anamount in the range of about 10 to about 20 weight percent.
 47. Anoxidized sorbent composition in accordance with claim 41 furthercomprising expanded perlite.
 48. An oxidized sorbent composition inaccordance with claim 44 further comprising expanded perlite in anamount in the range of about 10 to about 20 weight percent.
 49. Areduced sorbent composition comprising: (a) zinc oxide; and (b) asubstitutional solid metal solution wherein said substitutional solidmetal solution is characterized by the formula M_(A)Zn_(B), wherein M isa promoter metal and A and B are each numerical values in the range of0.01 to 0.99.
 50. A reduced sorbent composition in accordance with claim49 wherein A is in the range of from about 0.50 to about 0.97 and B isin the range of from about 0.03 to about 0.50.
 51. A reduced sorbentcomposition in accordance with claim 50 wherein M is a metal selectedfrom the group consisting of nickel, cobalt, iron, manganese, copper,zinc, molybdenum, tungsten, silver, antimony, and vanadium.
 52. Areduced sorbent composition in accordance with claim 49 wherein A is inthe range of from about 0.80 to about 0.95 and B is equal to about(1−A).
 53. A reduced sorbent composition in accordance with claim 52wherein M is nickel.
 54. A reduced sorbent composition in accordancewith claim 49 wherein zinc oxide is present in an amount in the range ofabout 10 to about 90 weight percent and said substitutional solid metalsolution is present in an amount in the range of about 5 to about 80weight percent.
 55. A reduced sorbent composition in accordance withclaim 49 further comprising a promoter metal-zinc aluminatesubstitutional solid solution characterized by the formulaM_(Z)Zn_((1−Z))Al₂O₄, wherein M is said promoter metal and Z is anumerical value in the range of from 0.01 to 0.99.
 56. A reduced sorbentcomposition in accordance with claim 55 wherein M is a metal selectedfrom the group consisting of nickel, cobalt, iron, manganese, copper,zinc, molybdenum, tungsten, silver, antimony, and vanadium.
 57. Areduced sorbent composition in accordance with claim 55 wherein M isnickel.
 58. A reduced sorbent composition in accordance with claim 55wherein said zinc oxide is present in an amount in the range of about 10to about 90 weight percent, said substitutional solid metal solution ispresent in an amount in the range of about 5 to about 80 weight percent,and said promoter metal-zinc aluminate substitutional solid solution ispresent in an amount in the range of from about 2 to about 50 weightpercent.
 59. A reduced sorbent composition in accordance with claim 49further comprising expanded perlite.
 60. A reduced sorbent compositionin accordance with claim 54 further comprising expanded perlite in anamount in the range of from about 2 to about 50 weight percent.
 61. Areduced sorbent composition in accordance with claim 55 furthercomprising expanded perlite.
 62. A reduced sorbent composition inaccordance with claim 58 further comprising expanded perlite in anamount in the range of from about 2 to about 50 weight percent.
 63. Acomposition comprising desulfurized cracked-gasoline wherein saiddesulfurized cracked-gasoline comprises less than about 1 ppmw thiolcompounds and less than about 1 ppmw tetrahydrothiophene compounds. 64.Composition in accordance with claim 63 wherein said desulfurizedcracked-gasoline has a decrease in average octane number, as determinedby Δ(RON+MON)/2, of less than 3.5.
 65. Composition in accordance withclaim 63 wherein said desulfurized cracked-gasoline comprises less thanabout 0.5 ppmw thiol compounds and less than about 0.5 ppmwtetrahydrothiophene compounds.
 66. Composition in accordance with claim63 wherein said desulfurized cracked-gasoline comprises less than about1 ppmw dihydrobenzothiophene compounds.
 67. Composition in accordancewith claim 63 wherein said desulfurized cracked-gasoline has a decreasein average octane number, as determined by Δ(RON+MON)/2, of less than 3.68. Composition in accordance with claim 63 wherein said desulfurizedcracked-gasoline comprises less than about 25 ppmw sulfur. 69.Composition in accordance with claim 63 wherein said desulfurizedcracked-gasoline comprises less than about 15 ppmw sulfur.